N-benzyl-α-phenethylnitrone | 174714-00-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-benzyl-α-phenethylnitrone
• 英文别名: N-benzyl-3-phenylpropan-1-imine oxide
• CAS: 174714-00-2
• 化学式: C₁₆H₁₇NO
• 分子量: 239.317
• InChiKey: HPWRJNNTHCGXIO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  28.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-benzyl-α-phenethylnitrone 、 N-乙基苄胺 以 氘代苯 为溶剂， 反应 18.0h， 生成
  参考文献：
  名称：

  Catalysis through Temporary Intramolecularity: Mechanistic Investigations on Aldehyde-Catalyzed Cope-type Hydroamination Lead to the Discovery of a More Efficient Tethering Catalyst

  摘要：

  Mechanistic investigations on the aldehyde-catalyzed intermolecular hydroamination of allylic amines using N-alkylhydroxylamines are presented. Under the reaction conditions, the presence of a specific aldehyde catalyst allows formation of a mixed aminal intermediate, which permits intramolecular Cope-type hydroamination. The reaction was determined to be first-order in both the aldehyde catalyst (alpha-benzyloxyacetaldehyde) and the allylic amine. However, the reaction displays an inverse order behavior in benzylhydroxylamine, which reveals a significant off-cycle pathway and highlights the importance of an aldehyde catalyst that promotes a reversible aminal formation. Kinetic isotope effect experiments suggest that hydroamination is the rate-limiting step of this catalytic cycle. Overall, these results enabled the elaboration of a more accurate catalytic cycle and led to the development of a more efficient catalytic system for alkene hydroamination. The use of 5-10 mol % of paraformaldehyde proved more effective than the use of 20 mol % of a-benzyloxyacetaldehyde, leading to high yields of intermolecular hydroamination products within 24 h at 30 degrees C.

  DOI：

  10.1021/ja303320x
• 作为产物：
  描述：

  以 氘代苯 为溶剂， 反应 18.0h， 生成 N-benzyl-α-phenethylnitrone 、 N-乙基苄胺
  参考文献：
  名称：

  Catalysis through Temporary Intramolecularity: Mechanistic Investigations on Aldehyde-Catalyzed Cope-type Hydroamination Lead to the Discovery of a More Efficient Tethering Catalyst

  摘要：

  Mechanistic investigations on the aldehyde-catalyzed intermolecular hydroamination of allylic amines using N-alkylhydroxylamines are presented. Under the reaction conditions, the presence of a specific aldehyde catalyst allows formation of a mixed aminal intermediate, which permits intramolecular Cope-type hydroamination. The reaction was determined to be first-order in both the aldehyde catalyst (alpha-benzyloxyacetaldehyde) and the allylic amine. However, the reaction displays an inverse order behavior in benzylhydroxylamine, which reveals a significant off-cycle pathway and highlights the importance of an aldehyde catalyst that promotes a reversible aminal formation. Kinetic isotope effect experiments suggest that hydroamination is the rate-limiting step of this catalytic cycle. Overall, these results enabled the elaboration of a more accurate catalytic cycle and led to the development of a more efficient catalytic system for alkene hydroamination. The use of 5-10 mol % of paraformaldehyde proved more effective than the use of 20 mol % of a-benzyloxyacetaldehyde, leading to high yields of intermolecular hydroamination products within 24 h at 30 degrees C.

  DOI：

  10.1021/ja303320x

文献信息

• Photocatalytic Reductive Fluoroalkylation of Nitrones
  作者：Vyacheslav I. Supranovich、Vitalij V. Levin、Marina I. Struchkova、Alexander D. Dilman

  DOI：10.1021/acs.orglett.7b03987

  日期：2018.2.2

  A method for the addition of fluorinated groups to nitrones using an iridium photocatalyst and ascorbic acid as a stoichiometric reducing agent is described. The reaction proceeds through the generation of fluorinated radicals by single-electron reduction of fluorinated alkyl iodides with an iridium complex mediated by visible light. Besides perfluorinated reagents, partially fluorinated alkyl iodides

  描述了一种使用铱光催化剂和抗坏血酸作为化学计量还原剂将氟化基团添加至硝基的方法。该反应通过用可见光介导的铱络合物通过单电子还原氟化烷基碘来生成氟化自由基来进行。除了全氟化试剂之外，部分氟化的烷基碘也可以有效地用于产生产物，这是常规的亲核加成反应无法获得的。通过用锌还原，可以容易地将所得的羟胺转化为有价值的氟化胺。
• α,β‐Unsaturated Amides as Dipolarophiles: Catalytic Asymmetric <i>exo</i> ‐Selective 1,3‐Dipolar Cycloaddition with Nitrones
  作者：Ming Zhang、Naoya Kumagai、Masakatsu Shibasaki

  DOI：10.1002/chem.201702330

  日期：2017.9.12

  1,3-Dipolar cycloaddition is a commonly exploited method to access 5-membered chemical entities with a variety of peripheral functionalities and their stereochemical arrangements. Nitrones are isolable 1,3-dipoles that exhibit sufficient reactivity toward electron-deficient olefins in the presence of Lewis acids to deliver highly substituted isoxazolidines. Herein we document that α,β-unsaturated amides

  1,3-偶极环加成是访问具有多种外围功能及其立体化学排列的5元化学实体的一种常用方法。硝基是可分离的1，3-偶极，在路易斯酸的存在下对缺电子的烯烃表现出足够的反应性，以递送高度取代的异恶唑烷。在本文中，我们记录了在In（OTf）3 /双异羟肟酸催化体系中使用设计的7-氮杂二氢吲哚助剂有效活化了通常被认为在1,3-偶极反应歧管中几乎没有反应性的α，β-不饱和酰胺。广泛的底物范围和从产物中干净地去除7-氮杂二氢吲哚助剂突出了本催化方法的合成用途。
• Catalytic Asymmetric 1, 3-Dipolar Cycloaddition Reaction of Nitrones with α′-Phosphoric Enones by a Chiral Ligand- Copper(II) Triflate Complex
  作者：Kyoung-Chan Lim、Young-Taek Hong、Sunggak Kim

  DOI：10.1002/adsc.200700377

  日期：2008.2.22

  Using the C2-symmetric bis-oxazoline copper(II) catalyst 6f as a chiral Lewis acid, α′-phosphoric enones 2 undergo 1,3-dipolar cycloaddition with nitrones 3 to provide isoxazolidines 4 with very high enantioselectivity and endo/exo selectivity.

  使用C 2对称的双恶唑啉铜（II）催化剂6f作为手性路易斯酸，α'-磷酸烯酮2与硝酮3进行1,3-偶极环加成，以提供具有非常高的对映选择性和内/外选择性的异恶唑烷4。
• Reductive Bromodifluoromethylation of Nitrones Promoted by Visible Light
  作者：Igor A. Dmitriev、Vyacheslav I. Supranovich、Vitalij V. Levin、Alexander D. Dilman

  DOI：10.1002/ejoc.201900274

  日期：2019.7.14

  A method for the synthesis of bromodifluoromethyl‐substituted hydroxylamines by reductive fluoroalkylation of nitrones with CF2Br2 is described. The reaction is promoted by visible light and employs ascorbic acid as a stoichiometric reducing agent.

  描述了一种通过CF 2 Br 2对硝基进行还原性氟烷基化合成溴二氟甲基取代的羟胺的方法。该反应由可见光促进，并使用抗坏血酸作为化学计量的还原剂。
• Visible Light Promoted 2-Bromotetrafluoroethylation of Nitrones
  作者：Igor A. Dmitriev、Vyacheslav I. Supranovich、Vitalij V. Levin、Marina I. Struchkova、Alexander D. Dilman

  DOI：10.1002/adsc.201800802

  日期：2018.10.4

  A reaction of nitrones with 1,2‐dibromotetrafluoroethane affording bromodifluoroethyl‐substituted hydroxylamines is described. The process is performed in the presence of a ruthenium photocatalyst and ascorbic acid as a stoichiometric reducing agent and is mediated by blue light irradiation. The fluroalkylation products can undergo chemoselective transformations involving either N−O or C−Br bonds furnishing

  描述了硝酮与1,2-二溴四氟乙烷的反应，得到溴二氟乙基取代的羟胺。该方法在钌光催化剂和抗坏血酸作为化学计量还原剂的存在下进行，并由蓝光辐射介导。氟烷基化产物可经历涉及N-O或C-Br键的化学选择性转化，从而提供各种四氟化化合物。